Production of new high molecular



Patented Sept. 13, 1938 UNITED STATES P'ATENT. OFFICE PRODUCTION OF NEW HIGH MOLECULAR SULPHUR CONTAINING CONDENSATION PRODUCTS the-Main, Germany No Drawing. Application November 2, 1934. Se-

rial N0. 751,182. 1933 4 Claims.

The present invention relates to new condensation products which are valuable especially as assistants for the textile and related industries and a process of producing the said products.

We have found that valuable condensation products which are readily dispersible in water (which term includes also products soluble in water) can be obtained by causing "polyhydric alcohol substances" (i. e., polyhydric alcohols or the corresponding oxides obtainable therefrom by intramolecular splitting 06 of water or polyethers obtainable therefrom by intermolecular splitting off of water from several molecules thereof) to react with organic compounds containing at least one SH-group, if desired in the presence of catalysts, any free hydroxyl groups still present in the reaction product being caused to react with reactive-compounds if desired. As initial materials may be mentioned especially the aliphatic, cycloaliphatic, aromatic or mixed aliphatic aromatic compounds containing one or more SH-groups which contain at least 6 carbon atoms in the molecule and also mercaptans which are substituted by halogen atoms, or nitro, sulphonic, carbonyl, ether or ester groups. For example ethyl, butyl, amyl, heptyl, octyl, dodecyl, cetyl, octodecyl and oleyl mercaptans, 7,18-0ctodecane dimercaptan, cyclohexyl mercaptan, methylcyclohexyl mercaptan, thiophenols, thionaphthols, thiosalicylic acid, para-nitro-thiophenol and benzyl mercaptan are suitable.

Ethylene glycol, glycerine, ethylene oxide, glycide compounds, polyglycol ethers or polyglycerines, for example, are caused to act on the said mercaptans. The nature and amount of the initial materials to be employed for the condensation depends on the nature of the desiredfinal product. It is advantageous to employ the polyhydric alcohols 01' their oxides in such amounts or the polyglycol ethers or polyglycerines of such molecular sizes that at least one radicle contain ing 4 or 6 carbon atoms is introduced into the molecule of the initial materials containing the SH-group. The condensation is effected at ordinary, or preferably at elevated, temperature, such as from about to about 200 C., preferably between and C., if desired in a closed vessel underincreased pressure for exam-' ple from 1 to 18 atmospheres, and in the presence or absence of inert solvents or diluents, such as water, or aliphatic or aromatic hydrocarbons or halogenated hydrocarbons. It is advantageous to work in the presence of catalytically acting substances, such as caustic soda, caustic potash, sodium carbonate, ammonia, sodium ethylate',

In Germany November 10,

iCl. 260-151) potassium cthylate or bleaching earths. 'ihe amounts of these substances used are preferably between 0.1 to 1 per cent by weight of the mercaptan employed.

According to the said process it is possible to introduce any high molecular ether radicle into the compounds containing the SH-group. depending on the amount of polyhydric alcohol or the first caused to react with one or more molecular proportions of ethylene chlorhydrin and thenwith one or more molecular proportions of ethyl ene oxide or propylene oxide.

The products obtainable according to this invention are generally speaking soluble or readily dispersible in organic solvents, suchas alcohol, ether, acetone, chloroform, benzine, benzene and nitrobenzene, oils and fats and water. They have, in a" difierent degree depending on the initial materials selected and the amount of polyhydric alcohols or the like employed, a high wetting, foaming, washing and dispersing power as well as a protective colloid action, so that they may find wide employment in the textile, leather, lacquer, paper, rubber and like industries. For example they are suitable as additional agents in dyeing, printing, dressing, washing, fulling and other processes usual in the working up of textiles. The compounds obtainable according to this invention have a neutral reaction and are stable to electrolytes. They may therefore also be very advantageously employed in the manufacture of artificial silk as an addition to the spinning solutions or precipitating baths. By reason of their high emulsifying power and their good protective colloid action the products are organic or inorganic acids, such as aceticacid, V

butyric acid, lauric acid, stearic acid, oleic acid, sulphopalmitic acid, naphthenic acids, naphthoic employed. Further compounds which are suitable for such subsequent reaction are halogenparaiiins, chlorocarbcnic esters, chlorethane sulphonic acid and monochloracetic acid. The said condensation products may also be halogenated, in particular the terminal hydroxyl groups may be replaced by halogen atoms, the resulting halogen compounds then being caused to react with ammonia or amines or compounds containing hydroxyl groups or alcoholates. The products thus obtained constitute equally valuable assistants for the textile and related industries.

When the condensation products are used they may be combined with other suitable substances, and preparations may be made for this purpose which contain mixtures of these different substances. For example preparations containing the said condensation products together with soaps, saponine, sulphuric esters or true sulphonic acids of organic compounds, as for example Turkey red oils, sulphite cellulose waste liquor, sulphuric esters of alcohols of high molecular weight, reaction products of fatty acids or their derivatives or chlorocarbonic esters with taurine', hydroxyethane sulphonic acids or polypeptides, or polymerization products of ethylene oxide or condensation products of ethylene oxide with organic compounds which contain hydroxyl, carboxylic or amino groups in the molecule, glue, rubber-like substances, dextrine or cellulose ethers have very valuable properties. In many cases it is also of advantage to employ the new condensation products together with salts of inorganic'or organic acids and bases, as for example hydroxides of monovalent or divalent metals, or amine as for example mono-, diand triethanolamine or pyridine, or to add thereto for example common salt, Glaubers salt, waterglass, phosphateasodium acetate or ethanolamine tartrate. Mixtures of the said condensation products with organic solvents, bleaching agents, such as perborates or alkali metal peroxides, or other substances may also be readily prepared and employed with advantage in practice.

The following examples will further illustrate the nature of this invention but the invention is not restricted to these examples.

Emrnple 1 About gram-molecules of ethylene oxide are caused to act in a closed vessel at 140 C. in the presence of about 0.5 per cent of sodium methylate on each gram-molecule of a dodecyl mercaptan obtained by the reaction of dodecyl bromide with sodium hydrosulphide. A viscous, liquid, practically odorless product is obtained which is soluble in water and which probably corresponds to the formula:

It has a very high wetting power and an excellent emulsifying power for mineral oils, fatty oilsand fats. It is eminently suitable for washing wool, especially in alkaline liquors. By treatment with sulphonating agents, a product is obtained which is eminently suitable as a wetting and dispersing agent for the textile and leather industries.

Example 2 About gram-molecules of gaseous ethylene oxide are caused to act at about 120 C. in a stirring autoclave with each gram-molecule of oleyl mercaptan (obtainable by reacting oleyl bromide with sodium sulphhydrate) with an addition of 0.5 per cent of caustic soda of 40 Baum strength. The resulting product which corresponds probably to about the following formula:

C1aH35.S.CHz.CH2-- (O.CH2.CH2) a- O.CH2.CH2.0H

Example 3 gram-molecules of gaseous ethylene oxide are caused to act in a stirring autoclave at about 120 C. under a pressure of 5 atmospheres on each gram-molecule of cetyl mercaptan (obtainable by condensation of cetyl bromide with sodium sulphhydrate) in the presence of from about 0.5 to 1 percent of caustic soda. A wax-like product corresponding probably to about the following formula:

CisH33.S.CH2.CH2(O.CH2.CH2) 1a- O.CH2.CH2.0H

readily soluble in water, is thus obtained which may be very advantageously employed as a levelling agent in the dyeing of textiles with vat dyestuffs.

A product having similar properties is obtained by employing 20 gram-molecules of glycide instead of the ethylene oxide.

Example 4 1 molecular proportion of decylmercaptan (obtainable by the interaction of decylbromide and sodium hydrosulphide) is caused to react with 5 molecular proportions of ethylene oxide in the presence of 0.2 per cent of sodium methylate in a closed vessel at 160 C. The reaction product which is obtained in the form of a viscous yellow oil is readily soluble in water and yields strongly foaming aqueous solutions. .Such solutions (for example a solution containing 2.25 grams of the said condensation product and 1 gram ofcalcined sodium carbonate per liter of water) are eminently suitable for washing woolen piece goods.

Example 5 1 molecular proportion of decylmercaptan is dissolved in a solution of 1 molecular proportion of potassium hydroxide in anhydrous ethyl alcohol. Polyglycerine chloride obtained from 1 molecular proportion of a polyglycerine of the molecular weight 520 and 1 molecular proportion of hydrogen chloride is allowed to flow slowly into the said solution at about from 75 to 80 C. while stirring under reflux-condensation. The reaction mixture is stirred for some more hours at the same temperature whereupon the potassium chloride precipitated is separated oil and the ethyl alcohol removed by distillation. The brownish sirupy reaction productis readily soluble in water and yields strongly foaming and well wetting aqueous solutions. Such solutions (for example a solution containing 2 grams of the said condensation product per liter) are most suitable for washing wool containing suint whereby white loose wool is obtained.

Products of similar properties are obtained if dodecylmercaptan instead of decylmercaptan is reacted with polyglycerine chloride in the manner set forth above;

Example 6 If 1 molecular proportion of epichlorhydrin is reacted with the alcoholic solution of 1 molecular proportion of the potassium salt of decylmercaptan in an analogous manner as described in the preceding example, after separating the potassium chloride precipitated and after removal of the alcohol a semi-solid wax-like reaction product is obtained which may be used with advantage in the preparation of creams and ointments.

For instance from 1.5 parts by weight of the said reaction product, 4 parts of cetyl alcohol, 3 parts of wool fat, 3 parts of soft paraifin, 7 parts of Vaseline, 1 part of glycerine and 30 parts of water a very good obtained. 7 a r r v If 1 molecular proportion of chlorosulphonlc acid is allowed to act on an etherial solution of 1 molecular proportion of the reaction product obtained according to the first paragraph of the present example, after removal of the hydrogen chloride and of the ether a water-soluble acid sulphuric acid ester is obtained which after neutralization with diluted solutions of alkali hydroxide or with an organic amine may be employed with advantage as a washing and cleans- 30 ing agent.

What we claim is: 1. A process for the preparation of high moleccream for the skin may be ular thioethers which comprises mixing an aliphatio mercaptan having more than 8 carbon atoms in the molecule and containing at least one mercapto group with a 1,2-propylene oxide containing in the methyl residue a reactive group which does not react with the mercaptan.

2. A process for the preparation of high molecular thioethers which comprises mixing an unsaturated aliphatic mercaptan having more than 8 carbon atoms in the molecule'and containing at least one mercapto group with a 1,2-propy1ene oxide cantaining in the methyl residue a reactive group which does not react with the mercaptan.

3. A process for the preparation of high molecular thioethers which comprises mixing an'aliphatic mercaptan having more than 8 carbon atoms in the molecule and containing two mercapto groups with a 1,2-propylene oxide containing in the methyl residue a reactive group which does not react with the mercaptan.

4. A process for the preparation of high-molecular thioethers which comprises mixing a 1,2- propylene oxide containing in the methyl residue a reactive group which does not take part in the reaction, with an aliphatic mercapto compound having more than 8 carbon atoms in the molecule and containing substituent groups which do not take part in the reaction.

HERMAN'N SCHUE'ITE. CONRAD SCHOELLER. MAXWITTWER. 

